Recovery of oxygen compounds from fischer-tropsch product



H. W. FLEMING sgpt. 29, 1953 RECOVERY OF OXYGEN COMPOUNDS FROM FISCHER-TROPSCH PRODUCT Filed June 27. 1949 |V mv :fom G I om N s I H E #mm .vm vu M wm M O M L lll.. V V W m V F mmv n u w mw d H a w u m. H u x NV 0m Al* mv md AI m NkhM .IAIIJ- IHII! J m. E IY, 3. m ../jmw mm w m v u m All .D N V u N |I| Nm m. O Z i l. 2 N o O O 1| O a B N n m m m 3 l a fwm mm N t w1 :i9 IHI... om .QN .nl am v1 ON i 11| w .8 PN M d n. 3 V I.. w fm- L WQ n l O w m a a 3 @u l! m o L Sw v m ATORNEVS Patented Sept. 29, 1953 RECOVERY OF OXYGEN COMPOUNDS FROM FISCHER-TROPSCH PRODUCT Harold W. Fleming, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Application June 27, 1949, Serial No. 101,656

17 Claims.

This invention relates to a process for treating normally liquid eluent resulting from the catalytic hydrogenation of a carbon oxide. In one aspect, this invention relates to the recovery of oxygenated organic compounds formed as by-products when hydrocarbons are synthesized from carbon monoxide and hydrogen. In another specic aspect, this invention relates to a process for separating the normally liquid oxygenated compounds resulting from the catalytic hydro:- genation of carbon oxide into one group containing those oxygenated compounds more soluble in water than in hydrocarbons and into a second group containing those oxygenated compounds more soluble in hydrocarbons than in Water. In one embodiment, this invention relates to a process for separating the normally liquid oxygenated compounds resulting from the hydrogenation of carbon monoxide in the presence of a uidized iron catalyst into one group containing low-boiling oxygenated compounds and into a second group containing higher boiling oxygenated compounds.

In the catalytic hydrogenation of a carbon oxide, a product comprising hydrocarbons and oxygenated hydrocarbon derivatives is obtained in relative yields dependent upon the choice of catalyst and of hydrogenation conditions. For example, hydrogen and carbon monoxide may be passed into a catalytic zone containing an iron catalyst suitable for the production of hydrocarbons as the principal reaction product'. During the reaction oxygenated organic compounds, water and carbon dioxide are also formed. The

total normally liquid product is readily separable into a hydrocarbon phase and an aqueous phase, and the oxygenated compounds are distributed throughout both phases. The aqueous phase contains oxygenated compounds which range in decreasing concentration from those that are completely miscible with Water to those that are only slightly soluble in Water. The reverse is true in the h-ydrocarbon phase where the oxygenated compounds range in decreasing concentration from those that are completely immiscible with water to those that are completely miscible with water. Usually the concentration of oxygenated compounds in the aqueous phase varies fromy one to twelve per cent, and the concentration of oxygenated compounds in the hydrocarbon phase varies from one to fteen per cent, Bothconcentrations are dependent upon the operating conditions and upon the specific catalyst used. Even higher concentrations in both phases are obtainable by effecting the hydrogenation reac- 2 tion with an iron catalyst at a relatively low temperature within the range of' 190l to 225 C. and by using a hydrogen to carbon monoxide ratio in the synthesis gas feed of about 1:1.

The recovery of oxygenated organic corn-pounds from the hydrogenation reaction products is usually accomplished by condensation and separation of the normally liquid products into an aqueous phase and a hydrocarbon phasewith subsequent processing of each phase to recover the oxygenated org-anic compounds. Both phases contain oxygenated organic compounds, such as alcohols, aldehydes, ketones and acids, and some of the compounds are found in both phases. The number of individual compounds is large, and, consequently, the separation of the individual compounds presents a complex problem involving the use of many processing steps.

It is an object of this invention to provide a novel process for treating normally liquid effluent resulting from the catalytic hydrogenation of a carbon oxide.

It is another object of this invention to provide a novel process for recovering oxygenated organic compounds formed as by-products when hydrocarbons are synthesized from carbon monoxide and hydrogen.

It is a further object of this invention to provide a process for separating the oxygenated organic compounds resulting from such a synthesis into one group containing those compounds more soluble in Water than in hydrocarbons and into a second group containing those compounds more soluble in hydrocarbons than in Water.

It is a further object of this invention to provide a process for separating the normally liquid oxygenated compounds resulting from the hydrogenation of carbon monoxide in the presence of a fluidized iron catalyst into one group containing low-boiling oxygenated compounds and into a second group containing higherboiling oxygenateclv compounds.

It is a further object of this invention to provide a novel process for recovering individual oxygenated organic compounds resulting from the hydrogenation of carbon monoxide.

Additional objects of this invention will be readily apparent from my disclosure as it appears herein.

I have found that the oxygenated organic compounds produced during the synthesis of hyd'rocarbons from hydrogen and carbon monoxide can be recovered by a process that avoids the complexity of processing steps encountered in prior art practice. My invention makes use of gas is recycled to reactor' I via lines I and 2.

3 the tendency of the individua1 oxygenated compounds to concentrate in either the aqueous phase or the hydrocarbon phase, and, as a result of the partition relationship of the individual compounds, recovery thereof is markedly simplied.

A detailed understanding of my invention can be obtained from the description of the accompanying drawing hereinbelow. The drawing is schematic, and such conventional equipment as valves, pumps, compressors, etc. have not been included in the drawing in order to facilitate the understanding of my invention. The inclusion of such equipment is within the scope of my invention.

My invention is applicable to the normally liquid effluent resulting from the Fischer-Tropsch synthesis. This reaction is effected by contacting a gaseous mixture containing hydrogen and carbon monoxide in a molar ratio within the '3' range of 1:1 to 3:1, preferably 1.8: to 2.2:1, and more preferably 2:1, with a suitable catalyst at an elevated temperature and pressure. The catalyst is selected from the group containing iron, cobalt, nickel and ruthenium, and it may be used on an inert support, such as kieselguhr, and promoted with minor amounts of metallic oxides, such as the oxides of' alkali and alkaline earth metals, thoria, silica and the like. The catalyst may be used in a fixed bed operation, but the fluidized catalyst technique is preferred. Reaction temperatures and pressures are dependent upon the specific catalyst used. I prefer to use a finely divided, reduced iron catalyst promoted with oxides of potassium, aluminum and calcium since this type of catalyst generally produces larger quantities of oxygenated organic chemicals than other known catalysts for the reaction. With this preferred catalyst the synthesis reaction is effected at temperatures within the range of 295 to 320 C., at superatmospheric pressures up to 150 atmospheres and higher and at catalyst fiuidizing conditions.

Referring to Figure l, a hydrocarbon synthesis is effected in reactor I which contains a fluidized bed of a reduced iron catalyst. Snythesis gas containing hydrogen and carbon monoxide enter reactor I via line 2, and the reaction ei'luent passes via line 3 and condenser 4 to settler 5. In

settler 5 the condensed reaction effluent stratifies into a liquid hydrocarbon phase, an aqueous phase and a gaseous phase. The gaseous phase contains low-boiling, normally gaseous hydrocarbons, carbon dioxide and unreacted carbon monoxide and hydrogen, and it is withdrawn from I settler 5 via line 6, and at least a portion of the If desired a portion of the gaseous phase may pass to a synthesis gas producing zone (not shown) for the production of additional quantities of hydrogen and carbon monoxide, and, alternatively, the hydrogen-rich gaseous phase may be used to regenerate catalyst that has become deactivated in reactor I.

The hydrocarbon phase containing normally liquid hydrocarbons, water-soluble and waterinsoluble oxygenated organic compounds passes from settler 5 via line 8 to topping zone 9, and in zone 9 the hydrocarbon phase is topped at a temperature such that substantially all the Watersoluble oxygenated compounds in the hydrocarbon phase are taken overhead. The topping temperature required is dependent upon the catalyst and operating conditions used in reactor I, and it is usually within the range of 150 to 200 C. I

prefer to use a temperature of 160 C., and the overhead fraction that boils below 160 C. passes from zone 9 via line I0 to an extraction step, to be described hereinbelow. The fraction of the hydrocarbon phase boiling above 160 C. passes from zone 9 via line I I to reactor i2 where the fraction s subjected to additional treatment, if desired. In reactor I2 the fraction boiling above 160 C. may be treated for removal of high-boiling, hydrocarbon soluble oxygenated compounds, for example, by liquid-liquid extraction with a glycol solvent, such as ethylene glycol or dicthyiene glycol, which selectively dissolves oxygenated organic compounds. Alternatively, in reactor I2 the fraction boiling above 160 C. may be passed in the vapor phase and at a temperature of 370 to 420 C. into contact with a catalyst, such as bauxite, magnesia or activated clay, which con- Verts the oxygenated compounds to hydrocarbons. An oxygen-free hydrocarbon product is then withdrawn from reactor I2 via line I3 as a product of the process, and it may then be fractionated to obtain desired hydrocarbon fractions, one of which may be a fraction boiling within the gasoline range.

The aqueous phase from settler 5 is withdrawn via line I4. A portion of the aqueous phase passes via line I5 to topping zone I6. It should be noted that topping zone I6 may be used only while the process is being started, since an aqueous mixture substantially identical to the topped aqueous phase from zone I6 is obtained and recycled from a subsequent step in my process for use in extractor II. In zone I6 the portion of' the aqueous phase therein is topped at a temperature above C., but below the boiling point o water at atmospheric conditions. I have found that a temperature of 98 C. is suitable. The overhead fraction from zone I6 is removed via line I8, and, since this fraction contains low-boiling oxygenated organic compounds, the overhead fraction may be treated, if desired, for the separation of those compounds. lThe topped fraction from Zone I6 which contains water and organic acids passes via line I9 to extractor I? where it contacts, preferably countercurrently, the overhead fraction from topping zone 9 which enters extractor I1 via line I0. Extractor I'I is operated at conditions such that liquid-liquid contacting is effected in the extraction zone. Atmospheric temperature and pressure are suitable for the extraction step, but higher and lower temperatures and pressures may be used, if desired. In extractor I1 the topped aqueous phase acts as an extracting solvent for extracting low-boiling oxygenated organic compounds from the overhead from zone 9. To effect the extraction in extractor II of oxygenated compounds from the hydrocarbon phase with the aqueous solvent, a volumetric ratio of aqueous solvent to hydrocarbon phase within the range of 0.511 to 2:1 is used.

From extractor I'I a raffinate phase, containing hydrocarbons and oxygenated organic coinpounds more soluble in hydrocarbons than in water and boiling not higher than C., is withdrawn via line 20 through which it passes to second extractor 2l. The solvent phase from extractor I'I, which contains water, organic acids and low-boiling oxygenated organic compounds more soluble in water than in hydrocarbons is withdrawn via line 22, and it passes along with aqueous phase from settler 5, passing in lines I4 and 23, to extractor 2I. In extractor 2I the raflinate phase from extractor I1 is used as the solvent to extract from the aqueous phase oxyammi 5 mated compounds more .soluble in hydrocarbons :in water. .Countercuzrrent liquid-.liquid extraction is @preferably usedmextractor 2l, :and :the temperature fand pressure 'are similar to those :used in extractor zll. In order to eiect the desired extraction in .extractor 2i a volumetric ratio of aqueous phase to hydrocarbon phase :higher than that 'used yextractor |31 iis employed. Generally, the `volumetric ratio 'falls within the range of 2:.3 to 4:11, and, Aif necessary to obtain a volumetric ratio within this expressed range, fresh water is introduced -to the :sy-stem via line 24. Alternatively, the fresh Water ,may .heintroduced directly to extractor 211 :ata singleipoint or multipontwise rorder te maintain the de- 2.

-sired volumetric ratio throughout the fox-tractor..

extractor f2! an :aqueous phase, .from which oxye-enated organic leonsipcunds .more soluble in hydrocarbons than in water have :been

extracted, 4is withdrawn ria huez-5. This aqueous phase contains, .in addition "to water, organic acids, and ,flow-boiling alcohols, aldehydes .and ketones. -The Aalcohols are butanol and flowerboiling alcohols; the l aldehydes areacetaldehyde and propionaldehyde; and the ketones are acc- .tone and methyl ethyl ketone. The aqueous phase passes via line 25 to ...topping-,zone Z6 which is operated at a temperature :below 'the boiling 'point of water 4and above the boiling point A.of an azeotrope of n-butyl alcohol and water, which is f.

92.4 C. at atmospheric pressure. -I have Afound a tempera-ture of 98 C. .to hesuitahle for topping the aqueous phase in yzone 26. The overhead Yfrom `zone .Z6 passes via ,line 2.1 to fractionator 28 `wherein .the overhead is fractionated and, thus, separated into components of the overhead. From ractionator v2.8 an overhead frac-tion con.- ,taining :acetaldehyde yand boiling at 20 YC. is withdrawn via line 2.9. .A ysecond Vtraction containing .an -azeotropic mixtune of propionaldehyde, acetone .and methyl alcohol, boiling from 45.4 to .56 C., is l,Withdrawn via line .30. A third fraction Ycontaining an vazeotropic mixture `of methyl ethyl ketone, ethyl .alcohol .and water,

boiling at 72 C., is withdrawn via .line 3l. Sepdrawn via line 35A A porton'of the `topped aquef ous phase passes via 4lines .35 ,and .l Ato.ex-tractor I1 where it is used as -the solvent, ,and in ex.- ,tractor .I1 vthe .topped aqueous .phase from zone `2.6 is used in lieu of topped aqueous phasevfrom zone I6. Topping zone I6 is not required for further operatio-n of my processfuntil it becomes necessary to .cease and thento recommence operation. Actually, topping Azone l5 is not essential ,to my process and it can be eliminated hy introducing to line 1.9 via line .31, fresh water containing organc .acids from ,an .outside source. Fresh water alone could be used, but it 'is preferred to use water containing organic acids, since .the organic acids enhance the .solvent powers of .the

water in .extractor I .1 and .the .organic acids in.-

hibit the `extraction of organic acids in .extractor l1 from the hydrocarbon phase into a dilute solvent phase.

Fro-m extractor 2l, a hydrocarbon phase containing oxygenated organic compounds more .-f

soluble l'1infhvImcarberxs .than in water is k.with-- drawn via :line 38.. 'This hvdrocarbonphase oon-.- tai-ns, in addition to norma-liv liquid hvdrocarhpns Aboiling nofhig-.her than 1.6.0 C., aldehvdescontain- 4ine more than three .carbon atoms per and alcohols retenes conta-ming .more .than Afour carbon atoms. ,per molecule. If it is desired to recover these oxveenated organic compounds. the hydrocarbon Aphase is passed 'view 'line ,3l-,to extractor 3i where it is contacted eountercurv rently in liquid-liquid extraction with .a portion of topped aqueous .phase from -zone 42li which enters .extractor .39 via lines 35 zand :49. The temperature and pressure lconditions in 'extractor :3 9 kare .similar to the conditions prevailing extractors I1 and 2|, and a volumetric ratio ,of aqueous phase to hydrocarbon phase in extractor 39 is maintained within the range of 1.:4 to 5 :1. vIn extractor n39 the aqueous phase solventl exe tracts oxygenated organic compounds from 'the hydrocarbon phase. Hydrocarbons, containing any unextracted oxygenated compounds, leave extractor 39 via line 41, and, if desired, the Oxy? genated organic compounds may 'be converted to the .corresponding hydrocarbons Ain reactor 42 which is similar to reactor il, described herein.- abnve. 'Hydrocarbons are removed via .line 43., :and suitable additional treatment, such as fractionation, can :be used :to :separate `the.hydrocarbon mixture into individual components Aof the mixture.

rThe concentration -rof'oxygenazted organic `com.- pounds in the hydrocarbon phase ,from :extractor :21 is relatively small, .and :in some operations it :may `be economically kundesirable .to extract the oxygenated compounds therefrom. In that event, the hydrocarbon phase may be passed :dfrectly to .reactor :42 via lines 3 8, H and Il :for .conversion .of fthe joxvgenated compounds to hy.- drocarbons.

Aqueous solvent yfrom :extractor Z39, containing, in addition to water, organic acids. alcohols higher boiling Vthan .butyl alcohol, 5a.*ldehydes higher boiling than propionaldhyde, and :ke- -tones higher :boiling than methyl ethyl ketone., is Awithdrawn via line 45 and passed to any :sui-t- .able means Afor vrecovering the oxygenated .com-

One method for eiecting the recovery involves passing aqueous solvent "viadine 1&5 to -saponier 'l5 lwhere organic acids and any yesters that .are present are converted tewater- .soluble metallic salts. vSodium hydroxide is 5a. .suitable saponifying agent, and sodium :salts of fthe vorganic acids and esters fare produced. Alter .saponicatlom the total effluent from vsaponlller 4i apasses via line .41 .to fractionator 4l from which the .alcohols .and ketones are recovered overhead vla line 4'9 with unpolymerized l.aide-- hydes. Sodium salts of the organic acids and water-insoluble polymers of the faldehydes are recovered via line 5U the lbottoms product from fractions-tor 48. Thefpolyrners may be separated iby iiltra'tion (not shown) and the sodium salts :are then reconverted to org-anic acids by treat- 'ment with amineral acid (by means not shown).

'In some instances, it will be unnecessary touse the .entire topped aqueous Vphase 'from lzone 28 in .extractors l1 `and 39, and, in that event, unre- .quired topped aqueous .phase is withdrawn trom ithe system via line '5!. The withdrawn portion contains organic acids, fand it may bexasdvisable to recover these acids by :methods known inthe art. On `the other har-1d, the topped aqueous phase ,from zone 2- 6 may, in some .-lnstanf, .be .insufficient for the Aextraction .steps .in extractors 7 l1 and I 9, and, in that event, fresh water is added to the system via line 31 and/or line 52.

In my disclosure hereinabove, I have referred to the oxygenated organic compounds as being either more soluble in water than in hydrocarbons or more soluble in hydrocarbons than in water. The oxygenated compounds that I extract either from hydrocarbons in extractor I1 or from water in extractor 2l are soluble both in hydrocarbons and in water, but each compound has a relatively higher solubility in one of hydrocarbons and water as compared with the other of these two solvents. The following table shows the solubilities of various oxygenated compounds in 100 parts of water at a temperature of 10 to 25 C.:

Table Propionaldehyde Butyraldehyde 4 Methyl ethyl ketone Methyl propyl ketone 4 N-butyl alcohol 9 N-amyl alcohol 2.7

The oxygenated organic compounds which I have termed lower-boiling and which are more soluble in water than in hydrocarbons are those compounds which have a solubility above iive parts in 100 parts of water at a temperature of 10 to 25 C. Those oxygenated organic compounds which are less soluble in water I have termed higher-boiling and they are more soluble in hydrocarbons than in water.

My disclosed process and invention are subject to various modifications which will fall within the scope of my invention.

Iclaim:

l. The process for treating normally liquid etlluent from the catalytic hydrogenation of a carbon oxide which comprises separating said ellluent into a hydrocarbon phase and an aqueous phase, separating from said hydrocarbon phase a fraction having an end boiling point in the range 150 C.-200 C. and comprising essentially hydrocarbons and oxygenated organic compounds more soluble in water than in hydrocarbons, directly contacting said fraction with water, recovering from said contacting step a hydrocarbon phase substantially free of normally liquid oxygenated organic compounds more soluble y in water than in hydrocarbons, directly contacting thus-recovered hydrocarbon phase with said aqueous phase separated from said reaction eiuent, and recovering from said last-named contacting step a hydrocarbon phase enriched with normally liquid oxygenated organic compounds more soluble in hydrocarbons than in water from said first-named aqueous phase and an aqueous phase substantially free of normally liquid oxygenated organic compounds more soluble in hydrocarbons than in water.

2. The process for treating normally liquid eflluent from the synthesis of org-anic compounds from hydrogen and carbon monoxide in the presence of a reduced iron catalyst which comprises separating said eluent into a hydrocarbon phase and an aqueous phase, separating from said hydrocarbon phase a fraction having an end boiling point in the range 150 C.-200 C. and comprising essentially hydrocarbons and oxygenated organic compounds more soluble in water than in hydrocarbons, directly contacting said fraction with water containing organic acids at liquid-liquid contacting conditions, recovering from said contacting step a hydrocarbon phase substantially free of normally liquid oxygenated organic compounds more soluble in water than in hydrocarbons, directly contacting thus-recovered hydrocarbon phase with said aqueous phase separated from said reaction eiiiuent at liquid-liquid contacting conditions, and recovering from said last-named contacting step a hydrocarbon phase enriched with normally liquid oxygenated organic compounds more soluble in hydrocarbons than in water from said first-named aqueous phase and an aqueous phase substantially free of normally liquid oxygenated organic compounds more soluble in hydrocarbons than in water.

3. A process for recovering normally liquid oxygenated organic compounds produced during the synthesis of organic compounds from hydrogen and carbon monoxide in the presence of a. fluidized reduced iron catalyst which comprises separating the normally liquid effluent from said synthesis reaction into a hydrocarbon phase and an aqueous phase, recovering from said hydrocarbon phase a fraction having an end boiling point in the range C-200 C. and comprising essentially hydrocarbons and oxygenated organic compounds more soluble in water than in hydrocarbons, directly contacting at liquid-liquid contacting conditions said hydrocarbon phase fraction with water containing organic acids, recovering from said contacting step a hydrocarbon phase from which oxygenated organic compounds more soluble in water than in hydrocarbons have been extracted, directly contacting at liquid-liquid contacting conditions thus-recovered hydrocarbon phase with said aqueous phase from said synthesis reaction elluent, recovering from said last-named contacting step a hydrocarbon phase enriched with normally liquid oxygenated organic compounds more soluble in hydrocarbons than in water from said first-named aqueous phase and an an aqueous phase containing normally liquid oxygenated organic compounds more soluble in water than in hydrocarbons, and separating from said thus-recovered aqueous phase a fraction containing lowboiling oxygenated organic compounds and boiling below 100 C.

4. A process according to claim 3 wherein the fraction recovered from the hydrocarbon phase of the normally liquid synthesis reaction eflluent has an end boiling point not higher than C.

5. A process according to claim 3 wherein the water containing organic acids for the rst contacting step is obtained by separating a fraction from a portion of the aqueous phase of the normally liquid synthesis reaction effluent having a boiling point above 80 C. but below 100 C.

6. A process according to claim 5 wherein the end boiling point of the fraction so-obtained is 98 C.

7. A process according to claim 3 wherein the aqueous solvent phase from the rst contacting step is admixed with the aqueous phase for the second contacting step.

8. A process according to claim 3 wherein the rst contacting step is effected with a volumetric ratio of aqueous solvent to hydrocarbon phase within the range of 0.5 l to 2:1.

9. A process according to claim 3 wherein the second contacting step is effected with a volumetric ratio of aqueous phase to hydrocarbon phase greater than in the first contacting step and within the range of 2 :3 to 4 1.

10. A process according to claim 3 wherein at least a portion of a fraction of the aqueous phase 9 from the last-named separating step from which low-boiling oxygenated organic compounds have been separated is recycled to the first-named contacting step.

11. A process according to claim 3 wherein at least a portion of a fraction of the aqueous phase from the last-named separating step from which low-boiling oxygenated organic compounds have been separated is contacted at liquid-liquid contacting conditions with hydrocarbon phase from the last-named contacting step and wherein an aqueous phase containing oxygenated organic compounds from said hydrocarbon phase is recovered and wherein oxygenated organic compounds are separated from the thus-recovered aqueous phase.

12. A process according to claim 11 wherein the volumetric ratio of aqueous phase to hydrocarbon phase in the contacting step is within the range of 1:4 to 5:1.

13. A process according to claim 3 wherein the oxygenated organic compounds more soluble in water than in hydrocarbons have a solubility above 5 parts in 100 parts of Water at a temperature of to 25 C. y

14. A process according to claim 13 wherein the oxygenated organic compounds comprise acetaldehyde, propionaldehyde, acetone, methyl ethyl ketone, methanol, ethanol, propanol and butanol.

15. A process according to claim 3 wherein the oxygenated organic compounds more soluble in hydrocarbons than in water have a solubility not above 5 parts in 100 parts of Water at a ternperature of 10 to 25 C.

16. A process according to claim 15 wherein the oxygenated organic compounds comprise aldehydes higher boiling than propionaldehyde, ketones higher boiling than methyl ethyl ketone and alcohols higher boiling than butanol.

17. 'I'he process for treating normally liquid effluent from the catalytic hydrogenation of a carbon oxide which comprises separating said eflluent into a liquid hydrocarbon phase and a liquid aqueous phase, separating from said hydrocarbon phase a fraction having an end boiling point in the range C.-200 C. and comprising essentially hydrocarbons and oXygenated organic compounds more soluble in water than in hydrocarbons, directly contacting said fraction with an aqueous solution boiling above 98 C. and containing organic acids, recovering from said contacting step a liquid hydrocarbon phase substantially free of normally liquid oXygenated organic compounds more soluble in water than in hydrocarbons, directly contacting said recovered liquid hydrocarbon phase with said separated liquid aqueous phase from said eiiuent, recovering from this contacting step a liquid hydrocarbon phase enriched with respect to normally liquid oxygenated organic compounds more soluble in hydrocarbons than in water and an aqueous phase substantially free of normally liquid oxygenated organic compounds more soluble in hydrocarbons than in water and separating from the above said aqueous phase an aqueous solution boiling above 98 C. and containing organic acids.

HAROLD W. FLEMING.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,476,788 White July 19, 1949 2,482,284 Michael et al Sept. 20, 1949 2,501,115 White Mar. 2l, 1950 2,505,752 Burton May 2, 1950 2,535,069 Johnson Dec. 26, 1950 

1. THE PROCESS FOR TREATING NORMALLY LIQUID EFFLUENT FROM THE CATALYTIC HYDROGENATION OF A CARBON OXIDE WHICH COMPRISES SEPARATING SAID EFFLUENT INTO A HYDROCARBON PHASE AND AN AQUEOUS PHASE, SEPARATING FROM SAID HYDROCARBON PHASE A FRACTION HAVING AN END BOILING POINT IN THE RANGE 150* C.-200* C. AND COMPRISING ESSENTIALLY HYDROCARBONS AND OXYGENATED ORGANIC COMPOUNDS MORE SOLUBLE IN WATER THEN IN HYDROCARBONS, DIRECTLY CONTACTING SAID FRACTION WITH WATER, RECOVERING FROM SAID CONTACTING STEP A HYDROCARBON PHASE SUBSTANTIALLY FREE OR NORMALLY LIQUID OXYGENATED ORGANIC COMPOUNDS MORE SOLUBLE IN WATER THAN IN HYDROCARBONS, DIRECTLY CONTACTING THUS-RECOVERED HYDROCARBON PHASE WITH SAID AQUEOUS PHASE SEPARATED FROM SAID REACTION EFFLUENT, AND RECOVERING FROM SAID LAST-NAMED CONTACTING STEP A HYDROCARBON PHASE ENRICHED WITH NORMALLY LIQUID OXYGENATED ORGANIC COMPOUNDS MORE SOLUBLE IN HYDROCARBONS THEN IN WATER FROM SAID FIRST-NAMED AQUEOUS PHASE AND AND AQUEOUS PHASE SUBSTANTIALLY FREE OF NORMALLY LIQUID OXYGENATED ORGANIC COMPOUNDS MORE SOLUBLE IN HYDROCARBONS THAN IN WATER. 